愈创木酚-β-D-葡萄糖苷的合成及其加香应用  

Synthesis of guaiacol-β-D-glucopyranoside and its flavoring application

作　　者：张改红 石栋栋 庞登红[2] 白冰 毛多斌 黄龙[2] ZHANG Gaihong;SHI Dongdong;PANG Denghong;BAI Bing;MAO Duobin;HUANG Long(School of Food and Bioengineering,Zhengzhou University of Light Industry,Zhengzhou 450002,Henan,China;China Tobacco Hubei Industrial Co.,Ltd.,Wuhan 430000,Hubei,China)

机构地区：[1]郑州轻工业大学食品与生物工程学院,河南郑州450002 [2]湖北中烟工业有限责任公司,湖北武汉430000

出　　处：《精细化工》2022年第10期2099-2103,2121,共6页Fine Chemicals

基　　金：河南省科技攻关计划项目(192102110212)。

摘　　要：以乙酰溴-α-D-葡萄糖(Ⅰ)和愈创木酚(Ⅱ)为原料,分别采用银盐法、相转移催化法和离子液体法,合成了愈创木酚-2,3,4,6-四-O-乙酰基-β-D-葡萄糖苷(Ⅲ);中间体Ⅲ脱去乙酰基得到了目标产物愈创木酚-β-D-葡萄糖苷(Ⅳ)。中间体及产物结构经^(1)HNMR、^(13)CNMR、FTIR和HRMS确认。通过TG-DSC和感官评吸分别考察了糖苷Ⅳ的热稳定性和加香效果。结果表明,3种方法均可得到中间体Ⅲ,离子液体法优于相转移催化法及银盐法。离子液体法的反应条件为:1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF_(4))为催化剂,无水K_(2)CO_(3)为缚酸剂,二氯甲烷为溶剂,n(Ⅱ)∶n(Ⅰ)∶n(催化剂)=1.0∶1.0∶0.3,室温反应4 h,在该条件下糖苷Ⅲ的收率为52.6%。糖苷Ⅲ在甲醇钠/甲醇体系中脱去乙酰基,得到目标糖苷Ⅳ,收率77.4%。TG-DSC结果表明,糖苷Ⅳ在228.0℃以下具有较好的热稳定性。将糖苷Ⅳ添加于卷烟中能改善香气品质。The target product guaiacol-β-D-glucoside(Ⅳ) was obtained from deacetylation of intermediate guaiacol-2,3,4,6-tetra-O-acetyl-β-D-glucoside(Ⅲ), which was synthesized from 2,3,4,6-tetra-O-acetyl-α-Dglucopyranosyl bromide(Ⅰ) and guaiacol(Ⅱ) by silver salt method, phase transfer catalysis method and ionic liquid method, respectively. The structures of intermediate Ⅲ and product Ⅳ obtained were firstly confirmed by ^(1)HNMR,^(13)CNMR, FTIR and HRMS. Then, the thermal stability and flavoring effect of target product Ⅳ were investigated by TG-DSC and sensory evaluation. The results showed that intermediate Ⅲcould be synthesized by all of the three above-mentioned methods with ionic liquid method superior to phase transfer catalysis and silver salt methods. The yield of intermediate Ⅲ produced by ionic liquid method reached 52.6% under the reaction conditions: 1-Butyl-3-methylimidazole tetrafluoroborate([bmim]BF_(4)) as catalyst, anhydrous potassium carbonate as acid binding agent, dichloromethane as solvent,n(Ⅱ) : n(Ⅰ) : n(catalyst)=1.0 : 1.0 : 0.3, room temperature and reaction time of 4 h. The glycoside Ⅳ obtained from acetyl group removal of intermediate Ⅲ in sodium methoxide/methanol system had a yield of 77.4%.TG-DSC result demonstrated that the targeted compound had good thermal stability below 228.0 ℃.Moreover, adding glycoside Ⅳ to cigarettes improved the aroma quality.

关 键 词：糖苷化 离子液体 愈创木酚-β-D-葡萄糖苷 热稳定性 加香 

分 类 号：O629.13[理学—有机化学]